Abstract
Parabens are ubiquitous, being found in surface waters around the world. Although little is known about the release of paraben transformation products and fate of transformation products in surface water. This study evaluates both parabens and paraben transformation products in the Brazos River upstream and downstream of a wastewater facility located in Waco, Texas. Concentrations of thirteen compounds were reported in this study, five parent parabens and eight paraben disinfection by-products. Analyte concentrations were spatially evaluated to determine if release of wastewater effluent affects their concentrations in the river. Two Brazos River tributaries were also sampled to determine if they released parabens and related compounds to the Brazos. Sampling occurred weekly for one year with at least 40 samples collected at each site. Analyses were completed for both yearly and seasonal data. Sites downstream of wastewater treatment outfalls had lower concentrations of methyl paraben during the yearly analysis and across multiple seasons in the seasonal analysis with average yearly annual methyl paraben concentrations decreasing from 0.83 ng/L at site 3 to 0.09 ng/L at site 4. Para-hydroxybenzoic acid was the compound present in greatest concentration at most sites across most seasons, with the highest average annual concentration of 10.30 ng/L at site 2. Spatial changes in para-hydroxybenzoic acid varied by season, with seasonal trends only identifiable after normalization by flow. Dichlorinated paraben concentrations increased in the river at sites downstream of wastewater treatment with a yearly average dichlorinated methyl paraben concentration of 0.490 ng/L at site 3 to 1.53 at site 4, just downstream of the major wastewater treatment plant. Concentration increases indicate that wastewater effluent contains sufficiently high dichlorinated paraben concentrations to effect concentrations downstream of effluent discharges. Dichlorinated species also persisted in the environment, with no significant decreases at sites further downstream during any season with an annual average dichlorinated methyl paraben concentration of 1.23 ng/L at site 6. Methyl paraben concentrations decreased at the site furthest downstream to a concentration of 0.081 ng/L, while dichlorinated methyl paraben concentrations remained stable with a concentration of 1.10 ng/L at the site furthest downstream. Due to the dichlorinated species being released in higher concentrations in effluent than parents and being more resistant to degradation, the dichlorinated parabens are more likely to be environmentally relevant than are parent parabens.
This is a preview of subscription content, log in via an institution to check access.
Data Availability
The data that support the finding of this study are available in an OSF repository at https://osf.io/2gvjp/?view_only=66ace57fc1f64e8f90c3eee1c265808c.
References
Abbas S, Greige-Gerges H, Karam N, Piet M-H, Netter P, Magdalou J (2010) Metabolism of parabens (4-Hydroxybenzoic Acid Esters) by hepatic esterases and UDP-glucuronosyltransferases in man. Drug Metab Pharmacokinet 25:568–577. https://doi.org/10.2133/dmpk.DMPK-10-RG-013
Albero B, Pérez RA, Sánchez-Brunete C, Tadeo JL (2012) Occurrence and analysis of parabens in municipal sewage sludge from wastewater treatment plants in Madrid (Spain). J Hazard Mater, Occur Fate Emerg Contaminant Municipal Wastewater Treatment Syst 239–240:48–55. https://doi.org/10.1016/j.jhazmat.2012.05.017
Arfaeinia H, Asadgol Z, Ramavandi B, Dobaradaran S, Kalantari RR, Poureshgh Y, Behroozi M, Asgari E, Asl FB, Sahebi S (2022) Monitoring and eco-toxicity effect of paraben-based pollutants in sediments/seawater, north of the Persian Gulf. Environ Geochem Health. https://doi.org/10.1007/s10653-021-01197-2
Chen J, Pycke BFG, Brownawell BJ, Kinney CA, Furlong ET, Kolpin DW, Halden RU (2017) Occurrence, temporal variation, and estrogenic burden of five parabens in sewage sludge collected across the United States. Sci Total Environ 593–594:368–374. https://doi.org/10.1016/j.scitotenv.2017.03.162
Czarczyńska-Goślińska B, Zgoła-Grześkowiak A, Jeszka-Skowron M, Frankowski R, Grześkowiak T (2017) Detection of bisphenol A, cumylphenol and parabens in surface waters of Greater Poland Voivodeship. J Environ Manage 204:50–60. https://doi.org/10.1016/j.jenvman.2017.08.034
Feng J, Zhao J, Xi N, Guo W, Sun J (2019) Parabens and their metabolite in surface water and sediment from the Yellow River and the Huai River in Henan Province: spatial distribution, seasonal variation and risk assessment. Ecotoxicol Environ Saf 172:480–487. https://doi.org/10.1016/j.ecoenv.2019.01.102
Galinaro CA, Spadoto M, de Aquino FWB, de Souza Pelinson N, Vieira EM (2022) Environmental risk assessment of parabens in surface water from a Brazilian river: the case of Mogi Guaçu Basin, São Paulo State, under precipitation anomalies. Environ Sci Pollut Res 29:8816–8830. https://doi.org/10.1007/s11356-021-16315-x
Gao Y, Ji Y, Li G, An T (2016) Theoretical investigation on the kinetics and mechanisms of hydroxyl radical-induced transformation of parabens and its consequences for toxicity: influence of alkyl-chain length. Water Res 91:77–85. https://doi.org/10.1016/j.watres.2015.12.056
Gomes JF, Leal I, Bednarczyk K, Gmurek M, Stelmachowski M, Diak M, Emília Quinta-Ferreira M, Costa R, Quinta-Ferreira RM, Martins RC (2017) Photocatalytic ozonation using doped TiO2 catalysts for the removal of parabens in water. Sci Total Environ 609:329–340. https://doi.org/10.1016/j.scitotenv.2017.07.180
Li W, Shi Y, Gao L, Liu J, Cai Y (2015) Occurrence, fate and risk assessment of parabens and their chlorinated derivatives in an advanced wastewater treatment plant. J Hazard Mater 300:29–38. https://doi.org/10.1016/j.jhazmat.2015.06.060
Li W, Gao L, Shi Y, Wang Y, Liu J, Cai Y (2016) Spatial distribution, temporal variation and risks of parabens and their chlorinated derivatives in urban surface water in Beijing, China. Sci Total Environ 539:262–270. https://doi.org/10.1016/j.scitotenv.2015.08.150
Lu J, Li H, Tu Y, Yang Z (2018) Biodegradation of four selected parabens with aerobic activated sludge and their transesterification product. Ecotoxicol Environ Saf 156:48–55. https://doi.org/10.1016/j.ecoenv.2018.02.078
Mao Q, Ji F, Wang W, Wang Q, Hu Z, Yuan S (2016) Chlorination of parabens: reaction kinetics and transformation product identification. Environ Sci Pollut Res 23:23081–23091. https://doi.org/10.1007/s11356-016-7499-y
Penrose M, Cobb G (2022) Identifying potential paraben transformation products and evaluating changes in toxicity as a result of transformation. WER 94:e10705. https://doi.org/10.1002/wer.10705
Penrose M, Cobb G (2023) Evaluating seasonal differences in paraben transformation at two different wastewater treatment plants in Texas and comparing parent compound transformation to byproduct formation. Water Res 235:11978. https://doi.org/10.1016/j.watres.2023.119798
Song H, Alfiya Y, Dubowski Y, Friedler E (2017) Sorption and biodegradation of propylparaben in greywater by aerobic attached-growth biomass. Sci Total Environ 598:925–930. https://doi.org/10.1016/j.scitotenv.2017.04.032
Svobodova A, Walterova D, Vostalova J (2006) Ultraviolet light induced alteration to the skin. Biomed Pap Med Fac Univ Palacky Olomouc Czech Repub 150:25–38. https://doi.org/10.5507/bp.2006.003
Talrose, V., Yermakov, A., Usov, A., Goncharova, A., Leskin, A., Messineva, N., Trusova, N., Efimkina, M., n.d. NIST Standard Reference Data Program, NIST Standard Reference Database Number 69. NIST Chemistry Workbook, Gaithersburg MD, 20899.
Tay KS, Rahman NA, Abas MRB (2010a) Ozonation of parabens in aqueous solution: kinetics and mechanism of degradation. Chemosphere 81(11):1446–1453. https://doi.org/10.1016/j.chemosphere.2010.09.004
Tay KS, Rahman NA, Abas RB, Mhd., (2010b) Kinetic studies of the degradation of parabens in aqueous solution by ozone oxidation. Environ Chem Lett 8:331–337. https://doi.org/10.1007/s10311-009-0229-7
Valkova N, Lepine F, Valeanu L, Dupont M, Labrie L, Bisaillon J-G, Beaudet R, Shareck F, Villemur R (2001) Hydrolysis of 4-hydroxybenzoic acid esters (Parabens) and their aerobic transformation into phenol by the resistant enterobacter cloacae strain EM. Appl Environ Microbiol 67:2404–2409. https://doi.org/10.1128/AEM.67.6.2404-2409.2001
Wu Y, Sun Q, Wang Y, Deng C, Yu C-P (2017) Comparative studies of aerobic and anaerobic biodegradation of methylparaben and propylparaben in activated sludge. Ecotoxicol Environ Saf 138:25–31. https://doi.org/10.1016/j.ecoenv.2016.12.017
Xu T, Chen J, Chen X, Xie H, Wang Z, Xia D, Tang W, Xie H-B (2021) Prediction models on p K a and base-catalyzed hydrolysis kinetics of parabens: experimental and quantum chemical studies. Environ Sci Technol 55:6022–6031. https://doi.org/10.1021/acs.est.0c06891
Yoom H, Shin J, Ra J, Son H, Ryu D, Kim C, Lee Y (2018) Transformation of methylparaben during water chlorination: effects of bromide and dissolved organic matter on reaction kinetics and transformation pathways. Sci Total Environ 634:677–686. https://doi.org/10.1016/j.scitotenv.2018.03.330
Acknowledgements
The authors would like to thank Chad Mansfield and Bianca Possamai for their part in sampling along the Brazos and Janelle Oldfather for helping process samples. The authors would also like to thank the Baylor Mass Spectrometry Center for providing access to the LC-MS used in analysis. The authors thankfully acknowledge financial support from the C. Gus Glasscock, Jr. Endowed Fund of Excellence in Environmental Sciences.
Funding
This work was supported by the C. Gus Glasscock, Jr. Endowed Fund of Excellence in Environmental Sciences.
Author information
Authors and Affiliations
Contributions
Michael Penrose designed experiments, conducted research, collected data, created figures and tables, and wrote the manuscript with input from George Cobb. George Cobb provided input and advice for experimental design, methodology, internal proposals and manuscript development.
Corresponding author
Ethics declarations
Conflicts of Interest
The authors have no conflicts of interest to disclose.
Supplementary Information
Below is the link to the electronic supplementary material.
Rights and permissions
Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.
About this article
Cite this article
Penrose, M.T., Cobb, G.P. Influences of Wastewater Treatment on the Occurrence of Parabens, p-Hydroxybenzoic Acid and Their Chlorinated and Hydroxylated Transformation Products in the Brazos River (Texas, USA). Arch Environ Contam Toxicol 85, 105–118 (2023). https://doi.org/10.1007/s00244-023-01025-x
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s00244-023-01025-x